磷杂菲基共聚协效阻燃聚酰胺6纤维的制备及其性能

doi:10.13475/j.fzxb.20210200108

摘要/Abstract

摘要：

为提高聚酰胺6(PA6)纤维的阻燃性能,以10-(2,5-二羧基苯氧基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPODP)为共聚阻燃剂,复配二硫化钼(MoS₂)或硫化锌(ZnS),制备DOPODP共聚协效阻燃PA6,经熔融纺丝制备阻燃PA6纤维,并对其结构、性能及阻燃机制进行研究。结果表明:DOPODP经共聚法成功引入PA6,DOPODP可提高PA6的阻燃性能,但其熔融温度、结晶温度等下降;引入协效阻燃剂后,阻燃PA6垂直燃烧(UL94)级别为V-0级,极限氧指数(LOI值)达30%以上;DOPODP对PA6主要表现为气相阻燃作用,DOPODP分解产生含磷自由基可捕获活性自由基,协效阻燃剂可促进PA6成炭;相比PA6纤维,阻燃PA6纤维力学性能下降,而织物的LOI值提高。

关键词: 聚酰胺6, 阻燃剂, 二硫化钼, 硫化锌, 共聚法, 阻燃纤维, 功能性纤维

Abstract:

In order to improve the flame retardancy of polyamide 6 (PA6) fibers,a flame retardant was synthesized by copolymerization with 10-(2,5-dicarboxyl phenoxyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPODP) and combination of molybdenum disulfide (MoS₂) or zinc sulfide (ZnS), the flame retardant PA6 fibers were prepared via melt spinning. The structure, properties, and the flame-retardant mechanism of the co-PA6 and its fibers were also studied. The results show that the DOPODP had been introduced into PA6 molecular chains, the flame retardancy of the copolymer was improved, but the melting temperature and crystallization temperature were reduced. The synergistic flame retardant PA6 achieved a V-0 rating according to the UL94 criterion with an LOI value greater than 30%. The study of the flame-retardant mechanism indicated that the DOPODP in PA6 mainly take effects in gas phase, DOPODP could decompose to phosphorus radicals. In addition, with the introduction of synergistic flame retardants, the char content of flame retardant PA6 was increased. Compared with PA6 fiber, the mechanical properties of flame retardant PA6 fibers were decreased, and the LOI value of the fabrics increased.

Key words: polyamide 6, flame retardant agent, molybdenum disulfide, zinc sulfide, copolymerization, flame retardant fiber, functional fiber

中图分类号:

TQ323.6

刘可, 陈爽, 肖茹. 磷杂菲基共聚协效阻燃聚酰胺6纤维的制备及其性能[J]. 纺织学报, 2021, 42(07): 11-18.

LIU Ke, CHEN Shuang, XIAO Ru. Preparation and properties of synergistic flame retardant copolyamide 6 fiber with phosphaphenanthrene group[J]. Journal of Textile Research, 2021, 42(07): 11-18.

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参考文献 18

[1]	ZHANG S M, FAN X S, XU C C, et al. An inherently flame-retardant polyamide 6 containing a phosphorus group prepared by transesterification polymerization[J]. Polymer, 2020, 207:122890. doi: 10.1016/j.polymer.2020.122890
[2]	GROH K J, BACKHAUS T, CARNEY-ALMROTH B, et al. Overview of known plastic packaging-associated chemicals and their hazards[J]. Science of the Total Environment, 2019, 651:3253-3268. doi: 10.1016/j.scitotenv.2018.10.015
[3]	LIU K, LI Y Y, TAO L, et al. Synjournal and characterization of inherently flame retardant polyamide 6 based on a phosphine oxide derivative[J]. Polymer Degradation and Stability, 2019, 163:151-160. doi: 10.1016/j.polymdegradstab.2019.03.004
[4]	LIU K, LI Y Y, TAO L, et al. Preparation and characterization of polyamide 6 fibre based on a phosphorus-containing flame retardant[J]. RSC Advances, 2018, 8(17):9261-9271. doi: 10.1039/C7RA13228J
[5]	LEE S H, OH S W, LEE Y H, et al. Preparation and properties of flame-retardant epoxy resins containing reactive phosphorus flame retardant[J]. Journal of Engineered Fibers and Fabrics, 2020, 15:1-8.
[6]	WEI P, LOU H J, WANG W, et al. Synjournal and properties of wholly aromatic phosphorus-containing thermotropic liquid crystal copolyesters with excellent fibre formation ability[J]. Liquid Crystals, 2020, 48(4):466-475. doi: 10.1080/02678292.2020.1789768
[7]	ZHANG J B, WANG X L, HE Q X, et al. A novel phosphorus-containing poly(1,4-cyclohexylenedimethylene terephthalate) copolyester: synjournal, thermal stability, flammability and pyrolysis behavior[J]. Polymer Degradation and Stability, 2014, 108:12-22. doi: 10.1016/j.polymdegradstab.2014.06.003
[8]	SHI X X, JIANG S H, ZHU J Y, et al. Establishment of a highly efficient flame-retardant system for rigid polyurethane foams based on bi-phase flame-retardant actions[J]. RSC Advances, 2018, 8(18):9985-9995. doi: 10.1039/C7RA13315D
[9]	PENG H Y, WANG D, ZHANG L P, et al. Amorphous cobalt borate nanosheets grown on MoS₂ nanosheet for simultaneously improving the flame retardancy and mechanical properties of polyacrylonitrile composite fiber[J]. Composites Part B: Engineering, 2020, 201:108298. doi: 10.1016/j.compositesb.2020.108298
[10]	LI A J, XU W Z, WANG G S, et al. Novel strategy for molybdenum disulfide nanosheets grown on titanate nanotubes for enhancing the flame retardancy and smoke suppression of epoxy resin[J]. Journal of Applied Polymer Science, 2018, 135(15):46064. doi: 10.1002/app.46064
[11]	JASNA V C, ANILKUMAR T, NAIK A A, et al. Chlorinated styrene butadiene rubber/zinc sulfide: novel nanocomposites with unique properties-structural, flame retardant, transport and dielectric properties[J]. Journal of Polymer Research, 2018, 25(6):144. doi: 10.1007/s10965-018-1536-0
[12]	周卫东, 余小伟, 陈龙, 等. 纤维级复合阻燃PA6的制备及其热稳定性研究[J]. 合成纤维工业, 2020, 43(3):16-21.
	ZHOU Weidong, YU Xiaowei, CHEN Long, et al. Preparation and thermal stability of fiber-grade composite flame retardant PA6[J]. China Synthetic Fiber Industry, 2020, 43(3):16-21.
[13]	MOURGAS G, GIEBEL E, SCHNECK T, et al. Syntheses of intrinsically flame-retardant polyamide 6 fibers and fabrics[J]. Journal of Applied Polymer Science, 2019, 136(31):47829. doi: 10.1002/app.v136.31
[14]	GE H, WANG W, PAN Y, et al. An inherently flame-retardant polyamide containing a phosphorus pendent group prepared by interfacial polymerization[J]. RSC Advances, 2016, 6(85):81802-81808. doi: 10.1039/C6RA17108G
[15]	LI Y Y, LIN Y Z, SHA K, et al. Preparation and characterizations of flame retardant melamine cyanurate/polyamide 6 composite fibers via in situ polymerization[J]. Textile Research Journal, 2017, 87(5):561-569. doi: 10.1177/0040517516632478
[16]	LEVCHIK S V, WEIL E D. Combustion and fire retardancy of aliphatic nylons[J]. Polymer International, 2000, 49(10):1033-1073. doi: 10.1002/(ISSN)1097-0126
[17]	YOUNIS A A. Optimization of mechanical, thermal, and ignition properties of polyester fabric using urea and phosphoric acid[J]. Journal of Industrial Textiles, 2020, 49(6):791-808. doi: 10.1177/1528083718798636
[18]	DUAN X C, YU B, YANG T H, et al. In situ polymerization of nylon 66/reduced graphene oxide nanocomposites[J]. Journal of Nanomaterials, 2018, 2018:1047985.

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试样编号	质量分数/%
试样编号	DOPODP	MoS₂	ZnS
0^#	0	0	0
1^#	3	0	0
2^#	5	0	0
3^#	7	0	0
4^#	9	0	0
5^#	9	2	0
6^#	9	0	2

试样编号	元素含量/%				磷含量/%		反应比/%
试样编号	C	H	N	O	理论	实测	反应比/%
0^#	63.02	9.94	12.20	14.84	—	—	—
1^#	63.13	9.70	11.86	14.99	0.230	0.221	96.09
2^#	63.21	9.67	11.89	14.86	0.387	0.371	95.87
3^#	63.45	9.53	11.80	14.71	0.536	0.512	95.52
4^#	63.59	9.48	11.75	14.55	0.697	0.635	91.10

试样编号	相对黏度	数均分子量/(g·mol^-1)	多分散性指数
0^#	2.52	2.19×10⁴	1.76
1^#	2.55	2.27×10⁴	1.79
2^#	2.47	2.18×10⁴	1.82
3^#	2.45	2.12×10⁴	1.84
4^#	2.37	1.92×10⁴	1.97
5^#	2.42	—	—
6^#	2.39	—	—

试样编号	熔融温度/℃	熔融焓/(J·g^-1)	结晶温度/℃	结晶度/%
0^#	221.3	71.7	182.7	37.6
1^#	218.4	56.7	179.4	29.7
2^#	214.8	56.3	176.4	29.5
3^#	211.5	55.4	171.4	29.1
4^#	209.5	52.5	157.9	27.6
5^#	210.1	53.4	179.9	28.5
6^#	209.1	57.3	166.7	30.6

试样编号	垂直燃烧		LOI值/%
试样编号	是否引燃脱脂棉	级别	LOI值/%
0^#	是	V-2	23.5±0.2
1^#	是	V-2	24.1±0.2
2^#	是	V-2	25.2±0.2
3^#	是	V-2	26.5±0.2
4^#	是	V-2	27.6±0.2
5^#	否	V-0	30.3±0.2
6^#	否	V-0	30.7±0.2